WO2015124710A1 - Composant vitrocéramique hautement homogène - Google Patents

Composant vitrocéramique hautement homogène Download PDF

Info

Publication number
WO2015124710A1
WO2015124710A1 PCT/EP2015/053576 EP2015053576W WO2015124710A1 WO 2015124710 A1 WO2015124710 A1 WO 2015124710A1 EP 2015053576 W EP2015053576 W EP 2015053576W WO 2015124710 A1 WO2015124710 A1 WO 2015124710A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
ceramic
cte
ceramic component
ppb
Prior art date
Application number
PCT/EP2015/053576
Other languages
English (en)
Inventor
Ralf Jedamzik
Steffen Grün
Thomas Lifka
Johann Faderl
Original Assignee
Schott Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102014002253.6A external-priority patent/DE102014002253A1/de
Application filed by Schott Ag filed Critical Schott Ag
Priority to RU2016137478A priority Critical patent/RU2681015C2/ru
Priority to EP15705614.4A priority patent/EP3107871B1/fr
Priority to CN201580009500.4A priority patent/CN106029594B/zh
Priority to JP2016553412A priority patent/JP7038473B2/ja
Publication of WO2015124710A1 publication Critical patent/WO2015124710A1/fr
Priority to US15/243,078 priority patent/US11465933B2/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/18—Mountings, adjusting means, or light-tight connections, for optical elements for prisms; for mirrors
    • G02B7/181—Mountings, adjusting means, or light-tight connections, for optical elements for prisms; for mirrors with means for compensating for changes in temperature or for controlling the temperature; thermal stabilisation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/60—Substrates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties

Definitions

  • the present invention relates to a glass-ceramic component having a low average coefficient of thermal expansion (CTE) and a high CTE homogeneity, to the use of such a component and to a process for producing such a component.
  • CTE coefficient of thermal expansion
  • Zerodur® is a lithium aluminosilicate glass-ceramic with a particularly low thermal expansion and a high stability.
  • Zerodur® is used as base material for a multiplicity of precision applica- tions, for example for producing mirrors for telescopes with large dimensions, but which is also used for producing smaller precision components, for instance stages for microlithography.
  • Zerodur® is commercially available in the following expansion classes:
  • a process for casting large homogeneous glass blocks as green glass for producing large glass-ceramic blocks is known from DE 102004052514A1 .
  • the method described in said application can be used to produce glass-ceramic components having a CTE homogeneity of up to 10 ppb/K, as are commercially available at the time of filing:
  • the above homogeneity tolerances mean e.g. that for Zerodur® components of more than 0.3 tons, a CTE (0;50) homogeneity of less than 10 ppb/K is not commercially available, up to 6 tons only a homogeneity of at most 20 ppb/K can be guaranteed. Even for small components of up to 0.3 tons, a CTE homogeneity of better than 6 ppb/K was not commercially available.
  • EUV (Extreme UV) lithography requires substrates for masks and mirrors which have an average CTE of less than 0 ⁇ 5 ppb/K in the temperature range of, for example, 19 to 25°C and have a CTE homogeneity of 6 ppb/K or better.
  • a glass-ceramic component which, at an application temperature T A , has a CTE, preferably an average CTE, in the interval of 0 ⁇ 20 ppb/K, preferably in the interval of 0 ⁇ 15 ppb/K, more preferable in the interval of 0 ⁇ 10 ppb/K, according to specific embodiments in the interval of 0 ⁇ 5 ppb/K, and a CTE homogeneity of at most 5 ppb/K, preferably at most 4 ppb/K, most preferably at most 3 ppb/K.
  • the invention relates to glass-ceramic components having a low average coefficient of thermal expansion or CTE ("Coefficient of Thermal Expansion").
  • CTE coefficient of Thermal Expansion
  • an "average CTE” is understood to mean the average of all CTE measurements carried out on a glass-ceramic component at various places.
  • a "low average CTE” is understood to mean the a CTE (0;50) of 0 ⁇ 100 ppb/K, preferably 0 ⁇ 50 ppb/K, more preferably 0 ⁇ 20 ppb/K, even more preferably 0 ⁇ 10 ppb/K and most preferably 0 ⁇ 7 ppb/K.
  • the average CTE for the temperature range of 0 to 50°C (CTE(0;50)) is usually reported. How- ever, the average CTE can also be reported for other temperature ranges. For high-precision applications, the average CTE is reported in a considerably smaller temperature range around the later application temperature, for example a CTE(19;25) for microlithography components. As described herein below, the average CTE can also be reported for a specific application temperature T A .
  • the average CTE for a temperature range can be determined by means of equation (1 ) below:
  • the length of a test specimen of a glass-ceramic is measured at the initial temperature t 0 , the test specimen is heated to a second temperature t and the length l t at this temperature is measured.
  • the average CTE [t 0 ; t] for the temperature range t 0 to t is obtained from the abovementioned formula (1 ).
  • the thermal expansion can be determined by means of dilatometry, i.e. the determination of the change in length of a test specimen as a function of the temperature.
  • An instrument for determining the average CTE is described, for example, in R. Mueller, K. Erb, R. Haug, A. Klaas, O. Lindig, G.
  • the CTE is determined as a function of the temperature for this measurement method.
  • the CTE(T) is then defined according to the formula (2) below:
  • the temperature-dependent change in length in the length of a test specimen from the initial length l 0 at the initial temperature t 0 to the length l t at the temperature t can be measured.
  • small temperature intervals of, for example, intervals of 5°C or 3°C are preferably chosen for determining a measurement point.
  • Such measurements can, for example, be carried out by dilatometric methods, interferometric methods, for example the method of Fabry-Perot, i.e.
  • the selected method for determining the ⁇ / ⁇ 0 - ⁇ measurement points preferably has a precision of preferably at least ⁇ 0.10 ppm, more preferably of ⁇ 0.05 ppm, most preferably of ⁇ 0.01 ppm.
  • a glass-ceramic is usually defined by the possible deviations from the CTE average which make it still usable for the planned application. This deviation from the average CTE is reported as a range (e.g. "0 ⁇ 10 ⁇ 10 "6 /K” or "0 ⁇ 10 ppb/K” for a range of from -10 to 10 ppb/K around an average CTE of 0 ppb/K).
  • a "low average CTE" is understood to be a value of at most 0 ⁇ 20 ppb/K, more preferably at most 0 ⁇ 10 ppb/K, most preferably at most 0 ⁇ 7 ppb/K, according to specific embodiments at most 0 ⁇ 5 ppb/K.
  • the glass-ceramic component has a high CTE homogeneity.
  • the value of the CTE homogeneity (“total spatial variation of CTE") is understood to mean what is termed the peak-to-valley value, i.e. the difference between the respective highest and the respective lowest CTE value of the samples taken from a glass-ceramic.
  • the CTE homo- geneity over the entire glass-ceramic component is at most 5 ppb/K, preferably at most 4 ppb/K, most preferably at most 3 ppb/K.
  • a glass-ceramic component can be characterized by the zero crossing of a CTE-T curve. If the zero crossing of the CTE-T curve of a glass-ceramic component lies at or in the proximity of the application temperature, the change in length given potential minor fluctuations in temperature around the application temperature is minimal. For precision applications, it is therefore generally the case that a glass-ceramic component having a zero crossing matched to the application temperature is used.
  • the position of the zero crossing of the CTE-T curve can be set by correspondingly adapting the ceramization of the glass-ceramic.
  • the CTE-T curve can have at least one zero crossing in a range of T A ⁇ 10 K, preferably T A ⁇ 5 K.
  • Preferred application temperatures lie in the range of -60 to 100°C, more preferably of -40°C to +80°C.
  • Particular embodiments of the present invention relate to glass-ceramic components for application temperatures T A of 22°C, 40°C, 60°C, 80°C and 100°C, which have a zero crossing of the CTE-T curve and/or tolerances as described above.
  • the CTE-T curve of the glass-ceramic has a gradient at the zero crossing of ⁇ 5 ppb/K 2 , more preferably ⁇ 2.5 ppb/K 2 , even more preferably ⁇ 2 ppb/K 2 .
  • Glass-ceramics for precision applications should also have a good internal quality. It is preferable for glass-ceramics to have at most 5 inclusions per 100 cm 3 , more preferably at most 3 inclusions per 100 cm 3 , most preferably at most 1 inclusion per 100 cm 3 .
  • inclusions are understood to mean both bubbles and crystallites having a diameter of more than 0.3 mm.
  • glass-ceramic components which have a diameter or an edge length of at most 800 mm and a thickness of at most 100 mm and which have at most 5 inclusions, preferably at most 3 inclusions, more preferably at most 1 in- elusion in each case per 100 cm 3 with a diameter of a magnitude of more than 0.03 mm.
  • the maximum diameter of the detected inclusions also serves as a measure of the internal quality.
  • the maximum diameter of individual inclusions in the overall volume of a glass-ceramic component having a diameter of less than 500 mm is preferably at most 0.6 mm, and preferably at most 0.4 mm in the critical volume for the application, for example in the proximity of the surface.
  • the maximum diameter of individual inclusions in glass-ceramic components having a diameter of 500 mm to less than 2 m is preferably at most 3 mm, and preferably at most 1 mm in the critical volume for the application, for example in the proximity of the surface.
  • Figure 1 shows the depiction of the two-dimensional measurement of the derivation of the CTE from the mean CTE value of a square glass-ceramic component having an area of 1.2 ⁇ 1.2 m edge length and a thickness of 225 mm according to Example 1 -B.
  • Figure 2 shows the depiction of the two-dimensional measurement of the CTE of a square glass-ceramic component having an area of 1.2 ⁇ 1.2 m edge length and a thickness of 225 mm and the position of the test specimens taken for the CTE homogeneity measurement of the glass-ceramic component according to Example 1 -B.
  • Figures 3 and 4 show the horizontal and, respectively, vertical distribution of the CTE values of the glass-ceramic component tested in respect of the CTE homogeneity.
  • Figure 5 shows the comparison of the CTE-T curves of a plurality of differently ceramicized glass-ceramic components, the zero crossings of the CTE-T curves of which lie between -10°C and +60°C.
  • FIG. 6 schematically shows the determination of the CTE (0;50).
  • a glass-ceramic is understood to mean inorganic, non-porous materials with a crystalline phase and a vitreous phase, with the matrix, i.e. the continuous phase, generally being a glass phase, i.e. a vitreous phase.
  • a transparent glass-ceramic is provided.
  • As a result of the transparency it is possible for many properties of such a glass-ceramic, in particular of course the internal quality thereof, to be assessed better.
  • a glass-ceramic composed of the system Li 2 0 - Al 2 0 3 - Si0 2 having the following composition (in % by weight based on oxide):
  • the glass-ceramic preferably has a proportion of Si0 2 of 50 to 70% by weight.
  • the proportion of Si0 2 is more preferably at most 62% by weight, even more preferably at most 60% by weight.
  • the proportion of Si0 2 is more preferably at least 52% by weight, even more preferably at least 54% by weight.
  • the proportion of Al 2 0 3 is preferably 17 to 32% by weight.
  • the glass-ceramic more preferably contains at least 20% by weight, even more preferably at least 22% by weight, Al 2 0 3 .
  • the proportion of Al 2 0 3 is more preferably at most 30% by weight, more preferably at most 28% by weight.
  • the phosphate content P 2 0 5 of the glass-ceramic is preferably 3 to 12% by weight.
  • the glass- ceramic more preferably contains at least 4% by weight, even more preferably at least 5% by weight, P 2 0 5 .
  • the proportion of P 2 0 5 is preferably limited to at most 10% by weight, more pref- erably to at most 8% by weight.
  • the glass-ceramic preferably also contains Ti0 2 in a proportion of 1 to 5% by weight, with preference being given to at least 1 .5% by weight Ti0 2 being present. However, the proportion is preferably limited to at most 4% by weight, more preferably to at most 3% by weight.
  • the glass-ceramic can also contain Zr0 2 in a proportion of at most 5% by weight, preferably at most 4% by weight. Zr0 2 is preferably present in a proportion of at least 0.5% by weight, more preferably at least 1 % by weight. Furthermore, the glass-ceramic can contain alkali metal oxides such as Li 2 0, Na 2 0 and K 2 0. Li 2 0 may be present in a proportion of at least 2% by weight, preferably at least 3% by weight. The proportion of Li 2 0 is limited to preferably at most 5% by weight, more preferably at most 4% by weight. Na 2 0 and K 2 0 are optionally present in the glass-ceramic.
  • the proportion of Na 2 0 and/or K 2 0 can in each case and independently be at most 2% by weight, preferably at most 1 % by weight, most preferably at most 0.5% by weight.
  • Na 2 0 and K 2 0 can in each case and in- dependency be present in a proportion of at least 0.01 % by weight, preferably at least 0.02% by weight, more preferably at least 0.05% by weight, in the glass-ceramic.
  • the glass-ceramic can also contain alkaline earth metal oxides such as MgO, CaO, BaO and/or SrO, and also further divalent metals such as ZnO.
  • the proportion of CaO is preferably at most 4% by weight, more preferably at most 3% by weight, even more preferably at most 2% by weight.
  • the glass-ceramic preferably contains at least 0.1 % by weight, more preferably at least 0.5% by weight, CaO.
  • MgO can be present in the glass-ceramic in a proportion of at most 2% by weight, preferably at most 1.5% by weight, and/or preferably at least 0.1 % by weight.
  • the glass-ceramics can contain BaO in a proportion of less than 5% by weight, preferably at most 4% by weight, and/or preferably at least 0.1 % by weight. In specific embodiments, the glass- ceramic may be BaO-free.
  • the glass-ceramics can contain SrO in a proportion of at most 2% by weight and/or preferably at least 0.1 % by weight. In specific embodiments, the glass-ceramic may be SrO-free.
  • the glass-ceramic preferably may contain ZnO in a proportion of preferably at least 1 % by weight, more preferably at least 1.5% by weight. The proportion of ZnO is limited to at most 4% by weight, preferably at most 3% by weight.
  • the glass-ceramic can also contain one or more customary refining agents such as As 2 0 3 , Sb 2 0 3 , SnO, S0 4 2" , F “ , CI “ , Br “ or a mixture of these in a proportion of at most 1 % by weight.
  • Transparent glass-ceramics with low coefficients of thermal expansion are known in this system, and commercially available products such as Zerodur®, Zerodur® M (both SCHOTT AG) and Clearceram® (Ohara) can be mentioned by way of example.
  • These glass-ceramics usually contain approximately 50 to 80% of solid solutions with a high quartz content, also known as ⁇ - eucryptite solid solutions, as the main crystal phase.
  • This crystallization product is a metastable phase which, depending on the crystallization conditions, changes its composition and/or structure or is converted into a different crystal phase.
  • the solid solutions with a high quartz content have a thermal expansion which is very low or even falls as the temperature rises.
  • One embodiment of the invention relates to glass-ceramic components having a large volume.
  • this term is intended to mean a glass-ceramic component having a mass of at least 500 kg, preferably at least 1 t, more preferably at least 2 t, in one embodiment of the invention at least 5 1, or edge lengths (width and/or depth) in the case of rectangular shapes of at least 0.5 m, more preferably at least 1 m, and a thickness (height) of at least 50 mm, preferably 100 mm, or in the case of round shapes a diameter of at least 0.5 m, more preferably at least 1 m, more preferably at least 1.5 m, and a thickness (height) of at least 50 mm, preferably 100 mm.
  • the glass-ceramic compo- nents can also be even larger glass-ceramic components having, for example, a diameter of at least 3 m or at least 4 m or greater and a weight of 10 to 15 tons.
  • the maximum size of the glass-ceramic components depends on the size of the melting tank. However, it is also possible to cast larger glass-ceramic components with a diameter of 8 m and having a weight of between 40 and 60 tons.
  • the invention also relates to rectangular glass-ceramic compo- nents, in which it is preferable that at least one surface has a surface area of at least 1 m 2 , preferably at least 1.2 m 2 , more preferably at least 1.4 m 2 .
  • a further embodiment of the present invention therefore relates to large- volume glass-ceramic components having high shape factors, which can lie between approximately 0.1 and 0.3 up to at most approximately 0.5.
  • a further embodiment relates to precision components with relatively small dimensions, in par- ticular in the case of rectangular shapes with edge lengths (width and/or depth) or in the case of round areas with diameters of at least 100 mm and/or less than 500 mm and a thickness of less than 50 mm, preferably less than 10 mm and/or at least 1 mm, more preferably at least 2 mm.
  • Precision components of this type can be used in microlithography, for example.
  • Components for microlithography are commonly used under standard clean room conditions, in particular at a room temperature of 22°C.
  • the CTE can be adapted to this application temperature.
  • components of this type are subjected to various process steps, for example coating with metallic layers, cleaning, patterning and/or exposure processes, in which temperatures which are higher than those that prevail during later use in the clean room are present. It is advantageous if a component of this type has a low thermal expansion not only at the later application temperature, but also under the thermal loading caused by the process steps.
  • the present invention therefore also relates to components in which the temperature interval which satisfies the CTE tolerance of 0 ⁇ 20 ppb/K, preferably of 0 ⁇ 15 ppb/K, more preferably 0 ⁇ 10 ppb/K, has at least an extent of 10 K, preferably at least 15 K, more preferably at least 20 K. Furthermore, according to this embodiment of the invention, preference is given to components having a CTE which is optimized to an application temperature of 20°C, 40°C, 50°C, 60°C and/or 80°C.
  • a glass-ceramic is generally produced as follows: suitable raw materials are melted in a suitable composition, refined, homogenized and then hot-formed to form a glass blank or green body or the green glass.
  • the "green body" of a glass-ceramic is understood to mean a vitreous body which has been melted from a suitable composition and which can be converted into a glass- ceramic by treatment with a suitable temperature programme.
  • the grain size distribution of the components of the batch may be advantageous to set. This can have an influence on the melting properties and should be selected such that it is possible to achieve unproblematic melting and therefore the most homogeneous melt possible. Surprisingly, it is not advantageous for good homogeneity to select all components in a particu- larly fine grain size.
  • a mixture of components of different grain sizes has proved to be advantageous, for example a division of the grain sizes of the components into at least two, for example three, classes. Division into 4 or 5 classes may also be advantageous.
  • the batch can comprise
  • a medium fraction having a grain size of a class 2 i.e. a mean grain diameter of 10 - 250 ⁇ , and 5 to 10% by weight of a coarse fraction having a grain size of a class 3, i.e. a grain diameter of 100 - 1000 m.
  • ni- trates carbonates or phosphates
  • oxides of the raw materials required, for example quartz powder, aluminium oxide, aluminium hydroxide, aluminium metaphosphate, aluminium orthophosphate, magnesium carbonate, magnesium phosphate, zirconium sand, zirconium oxide, zinc oxide, titanium dioxide, lithium carbonate, lithium nitrate, potassium carbonate and potassium nitrate.
  • the batch of the starting components is generally weighed out in charges.
  • a charge size which corresponds to approximately 10 to 25% by weight of the later quantity of the glass melt in the melting tank has proved to be expedient. It has surprisingly been found that smaller charge sizes can lead to an increase in the homogeneity of the glass- ceramic component when producing green glasses for glass-ceramic components of high homogeneity.
  • batch charges which correspond to less than 10% by weight, preferably less than 5% by weight, of the later quantity of the green glass melt in the melting tank are weighed out.
  • the weighing-out operation should be performed at least with an accuracy of preferably at least ⁇ 0.3% by weight, more preferably at least ⁇ 0.1 % by weight, most preferably at least ⁇ 0.05% by weight, since even relatively minor differences in composition and therefore the formation of striae (streaks) and deviations in homogeneity can be avoided by this measure.
  • the batch can be moistened, in or- der to avoid loss through carry-over in particular of finely particulate components.
  • at least 1 % by weight, more preferably at least 3% by weight, water can be added to the batch, for example. It is preferable for at most 10% by weight water to be added, however.
  • the water or OH content of the melt and therefore of the resulting glass-ceramic can be set by moistening the batch. It has surprisingly been found that a higher OH content can have an ad- vantageous effect on the homogeneity of a glass-ceramic. It is assumed that the presence of the water molecules makes the molecular bonds of the components in the melt less firm, and as a result the melt has a lower viscosity and can be homogenized more easily and more effectively. The relatively low viscosity can also bring about better refinement, and therefore it is possible to obtain glass-ceramic components with a particularly low number of bubbles.
  • Common LAS glass-ceramics have an OH content of approximately from 0.03 to 0.05 mol/l. It has been found that the setting of the OH content of the glass-ceramic to a content of at least 0.06 mol/l, more preferably at least 0.07 mol/l can prove to be advantageous for the CTE homo- geneity of a glass-ceramic.
  • the OH content is preferably at most 0.15 mol/l, more preferably at most 0.13 mol/l, further preferably at most 0.12 mol/l, further preferably at most 0.1 1 mol/l, further preferably at most 0.10 mol/l, further preferably at most 0.095 mol/l.
  • a plate of the glass-ceramic having a thickness of 0.57 mm was measured in an infrared spectrometer and the OH band of the IR spectrum was determined quantitatively between 2.7 and 3.3 ⁇ with respect to a calibration measurement and converted into the OH content.
  • the OH content of the melt can furthermore be set by hydrous starting components.
  • hydrous starting components it is preferred according to the invention not to use aluminium oxide but rather aluminium hydroxide in a proportion of at least 50% by weight, more preferably at least 80% by weight, of the total content of aluminium oxide as starting component.
  • exclusively aluminium hydroxide is used as starting component.
  • the OH content can also be set by using other hydroxides, for example Mg(OH) 2 , LiOH, KOH and/or other hydroxides.
  • the green glass is melted in a plurality of steps:
  • the melt can be homogenized by bubbling, by thermal means or by mechanical means.
  • Thermal homogenization here is understood to mean that the convection of the melt is promoted by increasing the temperature or different heating of the tank surfaces.
  • the temperature of the melt is increased to approximately 1600°C for the refining operation.
  • the melt can be kept at an elevated temperature for a number of days, with the duration of the holding time being dependent on the volume of the melt. It is assumed that the melt is further homogenized on a molecular level during such a holding or standing phase.
  • the green glass is cast in metal moulds, as are described, for example, in DE 102004052514A1 .
  • the casting mould is then moved away laterally from the region beneath the melting tank and moved into a furnace for controlled cooling.
  • the controlled cooling to room temperature is effected at a sufficiently low cooling rate in order to avoid stresses and the formation of cracks.
  • the glass block thus produced is preferably subjected to a visual inspection for freedom from bubbles, freedom from cracks, etc. This can be followed by a first machining operation, in particular the removal of the surface regions, before the ceramization of the green body to form the glass-ceramic is carried out.
  • the green glass or the glass or the green body is converted into a glass-ceramic by controlled volume crystallization.
  • crystallization nuclei of the same type or a different type are formed in the glass in a first conversion step ("crystallization nucleation").
  • Crystallization nuclei or crystal nuclei are understood to mean submicroscopic crystalline aggregates of a characteristic size.
  • crystal growth if appropriate at a slightly higher temperature, crystals or crystallites grow from the crystal nuclei.
  • the present invention also relates to the use of the glass-ceramic according to the invention in astronomy, for example as mirror supports for large segmented telescopes or monolithic astro- nomical telescopes or else ultra-light mirror substrates, as precision components, such as standards for precision measurement technology, mechanical precision parts, e.g. for ring laser gyroscopes, coil springs for the watchmaking industry, in LCD lithography, for example as mirrors and prisms, and also in microlithography, for example as mask holders, wafer stages and reference plates, and also as substrates for mask blanks and mirrors in EUV lithography.
  • precision components such as standards for precision measurement technology, mechanical precision parts, e.g. for ring laser gyroscopes, coil springs for the watchmaking industry
  • LCD lithography for example as mirrors and prisms
  • microlithography for example as mask holders, wafer stages and reference plates, and also as substrates for mask blanks and mirrors in EUV lithography.
  • the starting compounds named in Table 1 were weighed out with an accuracy of ⁇ 0.1 % by weight (% by weight, based on oxide). In this case, the size of the charge weight was 4% by weight of the total weight of the melt. Before being introduced into the melting tank, the batch was moistened with 8% by weight water.
  • This composition was melted in a melting tank measuring 28 m 3 for a period of time of several days, with the temperature being kept at approximately 1600°C.
  • the decomposition of As 2 0 3 in the process forms refining gases, which carry along small gaseous inclusions and homogenize the melt.
  • the glass melt is homogenized further.
  • controlling the temperature of the tank surface induces convection of the melt, in order to promote the homogenization.
  • the temperature of the glass melt is reduced to approximately 1400°C, and the latter is then cast into (a) cylindrical casting moulds having a diameter of 1550 mm and a height of 350 mm (Example 1 -A) and (b) rectangular casting molds having an edge length of 1 .3 m and a height of 350 mm (Example 1 -B).
  • the blocks of the green glass thus produced were ceramized under the following conditions after removal of the mar- ginal regions: firstly, the blank was heated at a heating rate of 0.5°C/h to a temperature of between 630 and 660°C.
  • Example 1 -A The heating rate was then reduced to 0.01 °C/h and heating was continued until a temperature of between 770 and 800°C was reached. This temperature was maintained for 80 hours. Then, the blank was cooled at a cooling rate of -1 °C/h to room temperature.
  • Example 1 -A The heating rate was then reduced to 0.01 °C/h and heating was continued until a temperature of between 770 and 800°C was reached. This temperature was maintained for 80 hours. Then, the blank was cooled at a cooling rate of -1 °C/h to room temperature.
  • a glass-ceramic plate having a diameter of 1 .5 m was cut from a cylindrical ceramized block (a), and the CTE homogeneity of said glass-ceramic plate was determined as described below. Furthermore, the CTE homogeneity of smaller rectangular glass-ceramic components having an area of 1 10 x 1 10 mm and, respectively, 150 ⁇ 1 10 mm was determined.
  • Example 1 -A Example 1 -A
  • Example 1 -A Example 1 -A
  • glass-ceramic comcylindrical form rectangular form rectangular form ponent diameter: 1 .5 m (150x 1 10x5)mm (1 10x1 10x5)mm height: 0.23 m
  • Test specimens were taken from the resulting glass-ceramics, the CTE-T curve of said test specimens being shown in Figure 5.
  • the glass-ceramic plates having edge lengths of 100 ⁇ 100 x 5 mm which were produced from these glass-ceramics likewise had a CTE homogeneity of 2 ppb/K.
  • Figure 1 shows a two-dimensional representation of the CTE homogeneity of the rectangular glass-ceramic component from Example 1 having edge lengths of 1.2 ⁇ 1.2 m.
  • Figure 2 shows the positions of the 64 test specimens taken. All CTE values measured lay between -15 and -10 ppb/K and thus correspond to CTE(0;50) 0 ⁇ 20 ppb/K. The CTE homogeneity was 5 ppb/K.
  • FIG. 3 shows the positions of the test specimens taken for this determination.
  • Figures 3 and 4 show CTE values for the individual test specimens of the test specimens taken in the horizontal ( Figure 3) and, re- spectively, in the vertical ( Figure 4) direction. The tolerances brought about by the measurement are shown in Figures 3 and 4.
  • the CTE homogeneity was 3 ppb/K (1 10 ⁇ 1 10 mm) and (150 ⁇ 1 10 mm), together 4 ppb/K.
  • a glass-ceramic raw glass melt was melted as described in Example 1 and cast into a round casting mould having a diameter of 4.5 m and a height of 350 mm. After cooling, the marginal regions were removed and the raw glass block was ceramized: firstly, the blank was heated at a heating rate of 0.5°C/h to a temperature of between 630 and 660°C. The heating rate was then reduced to 0.01 °C/h and heating was continued until a temperature of between 770 and 800°C was reached. This temperature was maintained for 80 hours. Then, the blank was cooled at a cooling rate of -1 °C/h to room temperature.
  • a round glass-ceramic disc having a diameter of 4263 mm, a thickness of 80 mm and a weight of 2.89 ton was cut from the ceramized block, and the CTE homogeneity of said glass-ceramic disc was determined as described in the table below.
  • the glass-ceramic disc had the internal quality described in Table 5: Table 6:
  • a glass-ceramic raw glass melts was melted basically as described in Example 1 but with the differences as
  • the melts were cast into a cylindrical casting molds having a diameter of 1550 mm and a height of 350 mm and processed and ceramized into cylindrical glass ceramic blanks having a diameter of 1.5 m and a height of 350 mm as described in Example 1 -A.
  • the physical properties are also described in Table 7 below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

L'invention concerne un composant vitrocéramique présentant un coefficient de dilatation thermique (CTE) moyen faible et une homogénéité CTE élevée. L'invention concerne également l'utilisation de ce composant, ainsi qu'un procédé de production associé.
PCT/EP2015/053576 2014-02-21 2015-02-20 Composant vitrocéramique hautement homogène WO2015124710A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
RU2016137478A RU2681015C2 (ru) 2014-02-21 2015-02-20 Высокооднородная стеклокерамическая деталь
EP15705614.4A EP3107871B1 (fr) 2014-02-21 2015-02-20 Composant vitrocéramique hautement homogène
CN201580009500.4A CN106029594B (zh) 2014-02-21 2015-02-20 高均匀性玻璃陶瓷部件
JP2016553412A JP7038473B2 (ja) 2014-02-21 2015-02-20 高均一性ガラスセラミック素子
US15/243,078 US11465933B2 (en) 2014-02-21 2016-08-22 Highly homogeneous glass-ceramic component

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102014002253.6 2014-02-21
DE102014002253.6A DE102014002253A1 (de) 2014-02-21 2014-02-21 Hochhomogene Glaskeramikkomponente
DE102014211700.3 2014-06-18
DE102014211700 2014-06-18

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/243,078 Continuation US11465933B2 (en) 2014-02-21 2016-08-22 Highly homogeneous glass-ceramic component

Publications (1)

Publication Number Publication Date
WO2015124710A1 true WO2015124710A1 (fr) 2015-08-27

Family

ID=52544500

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/053576 WO2015124710A1 (fr) 2014-02-21 2015-02-20 Composant vitrocéramique hautement homogène

Country Status (6)

Country Link
US (1) US11465933B2 (fr)
EP (1) EP3107871B1 (fr)
JP (2) JP7038473B2 (fr)
CN (1) CN106029594B (fr)
RU (1) RU2681015C2 (fr)
WO (1) WO2015124710A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018111144A1 (de) 2017-05-26 2018-11-29 Schott Ag Präzisionskomponente
EP4059902A1 (fr) 2021-03-16 2022-09-21 Schott Ag Vitrocéramique ayant des caractéristiques spécifiques d'expansion thermique
WO2022194846A1 (fr) 2021-03-16 2022-09-22 Schott Ag Composant de précision euvl ayant un comportement de dilatation thermique spécifique
US11465933B2 (en) 2014-02-21 2022-10-11 Schott Ag Highly homogeneous glass-ceramic component
DE102022122790A1 (de) 2021-09-08 2023-03-09 Schott Ag Glaskeramik sowie Verfahren zur Herstellung einer Glaskeramik
DE102021125476A1 (de) 2021-09-30 2023-03-30 Schott Ag Verfahren zum Modifizieren zumindest eines Bereichs einer Oberfläche oder eines Abschnittes eines Substrates und Substrat
EP4339169A1 (fr) 2022-09-15 2024-03-20 Schott Ag Vitrocéramique ayant des caractéristiques de dilatation thermique spécifiques

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981458B (zh) * 2017-03-24 2020-05-22 武汉利之达科技股份有限公司 一种含腔体结构的三维陶瓷基板及其制备方法
CN108181244A (zh) * 2017-11-30 2018-06-19 彩虹（合肥）液晶玻璃有限公司 一种测定tft-lcd液晶基板玻璃配合料均匀度的方法
US11167375B2 (en) 2018-08-10 2021-11-09 The Research Foundation For The State University Of New York Additive manufacturing processes and additively manufactured products
CN113200678B (zh) * 2021-03-18 2022-06-10 常熟佳合显示科技有限公司 一种玻璃材料及其制备方法和其制品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1321440A2 (fr) * 2001-12-21 2003-06-25 Schott Glas Produit en verre céramique et procédé de sa fabrication
EP1516863A1 (fr) * 2003-09-19 2005-03-23 Kabushiki Kaisha Ohara Vitrocéramiques transparentes à expansion thermique ultra-faible
US20050197242A1 (en) * 2004-02-20 2005-09-08 Ina Mitra Glas ceramic having a low thermal expansion
DE102004052514A1 (de) * 2004-10-21 2006-05-04 Schott Ag Verfahren und Form zum Gießen von Glasblöcken
WO2011138340A2 (fr) * 2010-05-03 2011-11-10 Carl Zeiss Smt Gmbh Substrats pour miroirs de lithographie par ultraviolets extrêmes et production de ces miroirs

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1902432B2 (de) 1967-07-01 1976-10-14 Jenaer Glaswerk Schott & Gen., 6500 Mainz Transparente glaskeramiken mit einem thermischen ausdehnungskoeffizienten von 0 + 1,5 mal 10 hoch -7 /grad c der im bereich von -30 bis + 70 grad c wenig temperaturabhaengig ist
NL6808826A (fr) 1967-07-01 1969-01-03
US4172712A (en) * 1976-05-19 1979-10-30 Dart Industries Inc. Glass batch wetting and mixing apparatus
FR2564823B1 (fr) 1984-05-23 1991-08-23 Schott Glaswerke Materiau vitroceramique ayant un comportement specifique en dilatation thermique
JP2516537B2 (ja) * 1992-09-14 1996-07-24 株式会社オハラ 低膨張透明結晶化ガラス
JP2668057B2 (ja) 1994-09-13 1997-10-27 株式会社オハラ 低膨張透明ガラスセラミックス
JP2003535807A (ja) * 2000-06-20 2003-12-02 ショット、グラス、テクノロジーズ、インコーポレイテッド ガラスセラミック複合材
US20050003262A1 (en) * 2003-07-02 2005-01-06 Rajiv Doshi Solid-state fuel cell and related method of manufacture
JP4513486B2 (ja) * 2004-10-01 2010-07-28 旭硝子株式会社 ＴｉＯ２を含有するシリカガラスの製造方法
JP4933863B2 (ja) * 2005-10-25 2012-05-16 株式会社オハラ 結晶化ガラスおよび結晶化ガラスの製造方法
JP4977406B2 (ja) 2006-06-06 2012-07-18 株式会社オハラ 結晶化ガラス及び結晶化ガラスの製造方法
JP4976058B2 (ja) 2006-06-06 2012-07-18 株式会社オハラ 結晶化ガラスおよび結晶化ガラスの製造方法
JP5428323B2 (ja) * 2007-12-27 2014-02-26 旭硝子株式会社 ＴｉＯ２を含有するシリカガラス
JP5470703B2 (ja) * 2007-12-27 2014-04-16 旭硝子株式会社 Ｅｕｖｌ用光学部材およびその表面処理方法
FR2932897B1 (fr) * 2008-06-20 2010-07-30 Europ De Systemes Optiques Soc Procede de faconnage d'un element optique aspherique
JP2010135732A (ja) 2008-08-01 2010-06-17 Asahi Glass Co Ltd Ｅｕｖマスクブランクス用基板
JP5187060B2 (ja) * 2008-08-13 2013-04-24 旭硝子株式会社 Ｅｕｖリソグラフィ用反射型マスクの製造方法
DE102008050263C5 (de) * 2008-10-07 2020-01-02 Schott Ag Transparente, eingefärbte Kochfläche mit verbesserter farbiger Anzeigefähigkeit und Verfahren zur Herstellung einer solchen Kochfläche
DE102009011850B3 (de) 2009-03-05 2010-11-25 Schott Ag Verfahren zum umweltfreundlichen Schmelzen und Läutern einer Glasschmelze für ein Ausgangsglas einer Lithium-Aluminium-Silikat(LAS)-Glaskeramik sowie deren Verwendung
DE102009043680A1 (de) * 2009-09-30 2011-03-31 Heraeus Quarzglas Gmbh & Co. Kg Rohling aus Titan-dotiertem, hochkieselsäurehaltigem Glas für ein Spiegelsubstrat für den Einsatz in der EUV-Lithographie und Verfahren für seine Herstellung
JP5762677B2 (ja) * 2009-09-30 2015-08-12 株式会社オハラ 結晶化ガラスの製造方法
JP5650387B2 (ja) * 2009-09-30 2015-01-07 株式会社オハラ 結晶化ガラス
EP2343586A1 (fr) 2009-12-30 2011-07-13 Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO Module de miroir à forme stabilisée et procédé de stabilisation d'un élément réflectif
US8767174B2 (en) * 2010-02-18 2014-07-01 Nikon Corporation Temperature-controlled holding devices for planar articles
WO2011105517A1 (fr) * 2010-02-24 2011-09-01 国立大学法人東北大学 Procédé de production d'un verre à ultra-faible expansion
DE102011008953B4 (de) 2011-01-19 2020-08-20 Schott Ag Substrat mit Leichtgewichtsstruktur
FR2977010B1 (fr) * 2011-06-27 2013-07-12 Sunpartner Sas Concentrateur solaire comprenant un heliostat et une lentille de fresnel
EP2881374B1 (fr) 2013-12-09 2017-09-27 Schott AG Composant pour des applications à basse température
CN106029594B (zh) 2014-02-21 2022-06-24 肖特股份有限公司 高均匀性玻璃陶瓷部件
US10377675B2 (en) * 2016-05-31 2019-08-13 Goodrich Corporation High temperature oxidation protection for composites

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1321440A2 (fr) * 2001-12-21 2003-06-25 Schott Glas Produit en verre céramique et procédé de sa fabrication
EP1516863A1 (fr) * 2003-09-19 2005-03-23 Kabushiki Kaisha Ohara Vitrocéramiques transparentes à expansion thermique ultra-faible
US20050197242A1 (en) * 2004-02-20 2005-09-08 Ina Mitra Glas ceramic having a low thermal expansion
DE102004052514A1 (de) * 2004-10-21 2006-05-04 Schott Ag Verfahren und Form zum Gießen von Glasblöcken
WO2011138340A2 (fr) * 2010-05-03 2011-11-10 Carl Zeiss Smt Gmbh Substrats pour miroirs de lithographie par ultraviolets extrêmes et production de ces miroirs

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11465933B2 (en) 2014-02-21 2022-10-11 Schott Ag Highly homogeneous glass-ceramic component
DE102018111144A1 (de) 2017-05-26 2018-11-29 Schott Ag Präzisionskomponente
US10730787B2 (en) 2017-05-26 2020-08-04 Schott Ag Precision component
WO2022194840A1 (fr) 2021-03-16 2022-09-22 Schott Ag Composants de précision ayant un comportement de dilatation thermique spécifique
DE102022105929A1 (de) 2021-03-16 2022-09-22 Schott Ag Glaskeramik mit spezifischem thermischen Ausdehnungsverhalten
WO2022194846A1 (fr) 2021-03-16 2022-09-22 Schott Ag Composant de précision euvl ayant un comportement de dilatation thermique spécifique
EP4059903A1 (fr) 2021-03-16 2022-09-21 Schott Ag Vitrocéramique ayant des caractéristiques spécifiques d'expansion thermique
DE102022105930A1 (de) 2021-03-16 2022-09-22 Schott Ag Glaskeramik mit spezifischem thermischen Ausdehnungsverhalten
EP4059902A1 (fr) 2021-03-16 2022-09-21 Schott Ag Vitrocéramique ayant des caractéristiques spécifiques d'expansion thermique
DE102022122790A1 (de) 2021-09-08 2023-03-09 Schott Ag Glaskeramik sowie Verfahren zur Herstellung einer Glaskeramik
DE102021125476A1 (de) 2021-09-30 2023-03-30 Schott Ag Verfahren zum Modifizieren zumindest eines Bereichs einer Oberfläche oder eines Abschnittes eines Substrates und Substrat
EP4339169A1 (fr) 2022-09-15 2024-03-20 Schott Ag Vitrocéramique ayant des caractéristiques de dilatation thermique spécifiques
DE102022123616A1 (de) 2022-09-15 2024-03-21 Schott Ag Glaskeramik mit spezifischem thermischen Ausdehnungsverhalten

Also Published As

Publication number Publication date
JP6899938B2 (ja) 2021-07-07
JP2017507106A (ja) 2017-03-16
JP2020111502A (ja) 2020-07-27
US11465933B2 (en) 2022-10-11
RU2681015C2 (ru) 2019-03-01
US20160355433A1 (en) 2016-12-08
CN106029594A (zh) 2016-10-12
CN106029594B (zh) 2022-06-24
RU2016137478A3 (fr) 2018-09-14
EP3107871B1 (fr) 2023-08-30
RU2016137478A (ru) 2018-03-28
JP7038473B2 (ja) 2022-03-18
EP3107871A1 (fr) 2016-12-28

Similar Documents

Publication Publication Date Title
US11465933B2 (en) Highly homogeneous glass-ceramic component
JP6945414B2 (ja) コーディエライトガラスセラミック、その製造および使用
JP4977406B2 (ja) 結晶化ガラス及び結晶化ガラスの製造方法
JP5690765B2 (ja) 光学ガラス、光学素子およびプリフォーム
JP2011136884A (ja) 光学ガラスの製造方法及び光学機器
EP4059903A1 (fr) Vitrocéramique ayant des caractéristiques spécifiques d'expansion thermique
US20180339933A1 (en) Precision component
JP2010006675A (ja) 光学ガラス、プリフォーム、及び光学素子
JP2017105703A (ja) 光学ガラス、プリフォーム及び光学素子
US20240002281A1 (en) Precision component with specific thermal expansion behavior
EP2871167A1 (fr) Verre cristallisé
JP2010006676A (ja) 光学ガラス、プリフォーム、及び光学素子
US20060135341A1 (en) B-quartz glass-ceramic extreme ultraviolet optical elements and a method of making them
JP2010195674A (ja) 光学ガラス、光学素子及び精密プレス成形用プリフォーム
US20230081248A1 (en) Glass ceramic and method for producing a glass ceramic
JP2003040641A (ja) ガラス用混合原料
JP2024042686A (ja) 特定の熱膨張挙動を示すガラスセラミックス
CN116282915A (zh) 耐高温玻璃及其制备方法、玻璃预制件和光学元件
TW201900576A (zh) 光學玻璃以及光學元件
DE102014002253A1 (de) Hochhomogene Glaskeramikkomponente

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15705614

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016553412

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2015705614

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015705614

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016137478

Country of ref document: RU

Kind code of ref document: A